含<strong>Cr</strong>耐蚀钢筋在模拟高碱性混凝土孔隙液中的钝化行为

doi:10.11900/0412.1961.2023.00203

金属学报

2025, Vol. 61

Issue (6): 929-940 DOI: 10.11900/0412.1961.2023.00203

研究论文

本期目录 | 过刊浏览

含Cr耐蚀钢筋在模拟高碱性混凝土孔隙液中的钝化行为

王慕亮¹^,², 孙玉朋¹^,², 陈磊¹^,², 魏洁²(

), 董俊华²(

)

1 中国科学技术大学材料科学与工程学院沈阳 110016
2 中国科学院金属研究所沈阳材料科学国家研究中心沈阳 110016

Passive Behavior of Corrosion-Resistant Cr-Containing Steel Bars in Simulated High-Alkaline Concrete Pore Solution

WANG Muliang¹^,², SUN Yupeng¹^,², CHEN Lei¹^,², WEI Jie²(

), DONG Junhua²(

)

1 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
2 Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

引用本文:

王慕亮, 孙玉朋, 陈磊, 魏洁, 董俊华. 含Cr耐蚀钢筋在模拟高碱性混凝土孔隙液中的钝化行为[J]. 金属学报, 2025, 61(6): 929-940.
Muliang WANG, Yupeng SUN, Lei CHEN, Jie WEI, Junhua DONG. Passive Behavior of Corrosion-Resistant Cr-Containing Steel Bars in Simulated High-Alkaline Concrete Pore Solution[J]. Acta Metall Sin, 2025, 61(6): 929-940.

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摘要:

针对不同Cr含量(0、3%和9%，质量分数)的耐蚀钢筋(20MnSi钢、3Cr钢和9Cr钢)在模拟高碱性混凝土孔隙液中的钝化行为，采用电化学测试技术(开路电位、EIS抗谱、极化曲线以及Mott-Schottky曲线)研究了钢筋表面钝化膜性能随时间的变化特征，并通过XPS对钝化膜成分与结构进行了分析。结果表明，在模拟高碱性混凝土孔隙液中，钢筋表面会生成层状结构钝化膜，钝化膜的结构、组成及保护性与钢筋中Cr元素含量和钝化时间密切相关。20MnSi钢钝化膜的外层主要为Fe(Ⅲ)化合物，内层主要为Fe(Ⅱ)氧化物；3Cr钢和9Cr钢钝化膜的外层由Fe(Ⅲ)和Cr(Ⅲ)的氧化物和氢氧化物组成，内层由Fe(Ⅱ)氧化物和Cr(Ⅲ)的化合物组成。3种钢筋形成的钝化膜在-0.8~0.2 V (vs SCE)电位区间内表现为n型半导体，且随浸泡时间增加，钝化膜中缺陷减少，钢的腐蚀电流密度减小，耐腐蚀性能有所提高。Cr含量越高，相同时间形成的钝化膜点缺陷密度越低，钝化膜越致密，钢筋耐腐蚀性能越好。

关键词 ：耐蚀钢筋, 混凝土模拟液, 钝化膜, 电化学测试

Abstract：

Reinforced concrete has become the preferred choice for modern building structures owing to its long durability, strong structure, flexible, and diverse designs, wide availability, and low cost. Traditional carbon steel bars are prone to corrosion in marine environments, resulting in problems such as steel bar breakage and concrete cracks, thereby affecting the safety and reliability of marine engineering structures. Therefore, using high-performance corrosion-resistant alloy steel bars can effectively solve the problem of steel corrosion in marine engineering and improve the durability and maintainability of engineering structures. Concrete is a highly alkaline environment when it is free from erosion, and the pH value of its pore solution is 12.5-13.6. When steel bars are exposed to this environment, a stable passive film forms on their surface. This spontaneously formed passive film can keep the steel bars in a passive state, preventing corrosion and considerably extending the service life of reinforced concrete structures. The differences in the composition and structure of the passive film on steel bars represent important reasons for the different corrosion resistance performances of steel bars in concrete. To study the passive behavior of corrosion-resistant rebars (20MnSi steel, 3Cr steel, and 9Cr steel) with different Cr contents (0, 3%, and 9%, mass fraction) in simulated high-alkaline concrete pore solution, electrochemical measurements (including open circuit potential, electrochemical impedance spectroscopy, polarization curve, and Mott-Schottky curve) were used to study the changes in the properties of the passive film on the surface of the rebars over time. XPS was used to analyze the composition and structure of the passive film. The results show that a passive layered film was formed on the surface of the rebars in the simulated high-alkaline concrete pore solution, and the structure, composition, and protective properties of the passive film were closely related to the Cr content and passivation time of the rebars. The passive film of 20MnSi steel was mainly composed of Fe(III) compounds in the outer layer and Fe(II) oxides in the inner layer. The outer layer of the passive film of 3Cr steel and 9Cr steel comprised Fe(III) and Cr(III) oxides and hydroxides, and the inner layer comprised Fe(II) oxides and Cr(III) compounds. The passive films formed by the three types of rebars exhibited n-type semiconductor properties within the potential range of -0.8 to 0.2 V (vs SCE). As the immersion time increased, the defect density in the passive film decreased, leading to decreased corrosion current density of the rebars and improved corrosion resistance. When the Cr content is increased, the point defect density of the passive film decreases. At the same time, the passive film becomes dense, resulting in improved corrosion resistance of the rebars.

Key words： corrosion-resistant steel bar concrete simulating solution passive film electrochemical test

收稿日期: 2023-05-06

ZTFLH:

TG174

基金资助:辽宁省科技重大专项项目(2020JH1/10100001)

通讯作者: 魏洁，jwei@imr.ac.cn，主要从事混凝土结构中钢筋的腐蚀与防护研究；
董俊华，jhdong@imr.ac.cn，主要从事耐蚀材料的电化学设计及腐蚀监检测研究

Corresponding author: WEI Jie, associate professor, Tel: 13478204310, E-mail: jwei@imr.ac.cn;
DONG Junhua, professor, Tel: 13842056525, E-mail: jhdong@imr.ac.cn

作者简介: 王慕亮，男，1998年生，硕士

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表1 20MnSi、3Cr和9Cr钢的名义成分 (mass fraction / %)

图1 热处理后3种钢筋显微组织的SEM像

图2 20MnSi、3Cr和9Cr钢在模拟混凝土孔隙液中开路电位随浸泡时间的变化

图3 20MnSi、3Cr和9Cr钢在模拟混凝土溶液中浸泡不同时间后的极化曲线(a) 20MnSi steel (b) 3Cr steel (c) 9Cr steel

图4 20MnSi、3Cr和9Cr钢在模拟混凝土溶液中浸泡不同时间后的腐蚀电流密度

图5 20MnSi、3Cr和9Cr钢在模拟液中浸泡不同时间后EIS结果

图6 用于EIS数据拟合等效电路

表2 20MnSi、3Cr和9Cr钢浸泡不同时间后等效电路的拟合参数

图7 20MnSi、3Cr和9Cr钢极化电阻(Rc)和电荷转移电阻(Ra)随时间变化曲线

图8 20MnSi、3Cr和9Cr钢在模拟混凝土溶液中浸泡不同时间后的Mott-Schottky (MS)曲线

表3 20MnSi、3Cr和9Cr钢在模拟混凝土溶液中浸泡不同时间后点缺陷密度 (1021 cm-3)

图9 20MnSi、3Cr和9Cr钢浸泡168 h后表面钝化膜不同溅射深度的XPS

图10 3种钢筋钝化膜中不同元素含量随溅射深度变化曲线

图11 模拟混凝土溶液中浸泡24和168 h后，20MnSi、3Cr和9Cr钝化膜中不同成分随溅射深度分布

图12 20MnSi、3Cr和9Cr钢在模拟混凝土孔隙液中钝化膜生长机制示意图

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